US4536179A - Implantable catheters with non-adherent contacting polymer surfaces - Google Patents

Implantable catheters with non-adherent contacting polymer surfaces Download PDF

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US4536179A
US4536179A US06/422,758 US42275882A US4536179A US 4536179 A US4536179 A US 4536179A US 42275882 A US42275882 A US 42275882A US 4536179 A US4536179 A US 4536179A
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Prior art keywords
catheter
coating
tubular elements
fluorocarbon
silicone rubber
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US06/422,758
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Michael H. Anderson
Christopher S. Lyons
Bruce D. Wigness
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University of Minnesota
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University of Minnesota
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/0043—Catheters; Hollow probes characterised by structural features
    • A61M25/0045—Catheters; Hollow probes characterised by structural features multi-layered, e.g. coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S128/00—Surgery
    • Y10S128/14—Polytetrafluoroethylene, i.e. PTFE
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S128/00—Surgery
    • Y10S128/21—Silicone

Definitions

  • This invention is directed to catheters adapted for long term implantation within living bodies and characterized by non-adherent contacting polymer surfaces.
  • polymer films are in close contact with polymer surfaces.
  • Two catheters of this type are disclosed in the copending Dorman application Ser. No. 245,379, filed Mar. 19, 1981, and the copending Wigness et al application Ser. No. 367,683, filed Apr. 12, 1982, hereafter referred to as the check valve catheter and the vascular access catheter, respectively. Both applications are of common ownership with the present application.
  • the preferred form of the check valve catheter consists of a thin silicone rubber sleeve stretched over a silicone rubber catheter. Silicone rubber surfaces in contact will adhere over time. This can result from the attraction of some compounds to chemically similar compounds and a knitting phenomenon where loose polymer chains at the surface become woven together. This adhesion greatly compromises the long term operation of the check valve catheter. During its development, a method of eliminating this adhesion was researched. A method of impregnating the rubber with a lubricant gave a temporary solution, but a permanent solid lubricant that would not leach out was desired. Films of graphite and albumin were sandwiched between the sleeve and the catheter but did not reduce adhesion significantly. Although silicone rubber has a low surface energy which is known to reduce adhesion, its ability to knit into a surface increases the actual surface contact causing a net increase of adhesion. For these reasons, a smooth film of lower surface energy than silicone rubber was desired.
  • the vascular access catheter consists of a flexible partition inside the catheter that can be shifted to one side to expose an inner lumen, thus enabling blood withdrawal or infusion.
  • it is made of silicone rubber and over time the contacting surfaces adhere to one another.
  • a fluorocarbon surface such as polytetrafluoroethylene (PTFE) is known to have the desired nonadhering qualities. Glow discharge plasma polymerization of fluorocarbons is the only method known to provide the conditions necessary to react fluorine groups with the inert methyl groups on the surface of silicone rubber.
  • PTFE polytetrafluoroethylene
  • Plasma polymerization of TFE has been widely studied in the last decade. Although most of the studies are aimed at understanding the process, a few specific applications have been cited and patents that include the process have been granted.
  • U.S. Pat. No. 4,125,152, granted on Nov. 14, 1978 discloses the use of plasma polymerization of TFE to prevent adherent scale deposition on heat transfer surfaces in contact with heat transfer fluids.
  • U.S. Pat. No. 4,100,113, granted on July 11, 1978 discloses the use of plasma polymerization of TFE in the preparation of electrolytic cell membranes by polymerization onto polymer substrates.
  • U.S. Pat. No. 3,703,585, granted on Nov. 21, 1972, discloses a process of sputtering PTFE polymer onto a substrate. This process differs from plasma polymerization of TFE in that a glow discharge using an inert gas such as argon is used to break off free radicals from the base material. The radicals are then able to deposit onto a substrate. This process has been studied for applying lubricant to small parts (K. G. Budinski, J. Vac. Sci. Technol. 12:786-789, 1975).
  • the invention is directed to catheters for long term implantation within living bodies which are composed of flexible inert non-toxic biocompatible polymeric material and which have surfaces in close face-to-face contact.
  • the catheters are characterized by a thin film glow discharge plasma polymerized fluorocarbon coating on at least one of the contacting surfaces.
  • the ultra-thin coating having a thickness in the range between about 50 and 1000 Angstroms prevents adhesion of cured polymer surfaces in contact and acts as a lubricant.
  • the films are smooth and pinhole-free so as to control or prevent diffusion into or out of the polymer substrate.
  • the films are biocompatible and do not change the bulk properties of the substrate materials.
  • plasma polymerization is achieved by producing an electric glow discharge in a gas at ranges of 30-300 mtorr of pressure.
  • a partially ionized gas or plasma is created when released electrons ionize the gas by inducing chain collisions.
  • Radio frequency of 13.56 Mhz is most often used.
  • audio frequency, 60 cycle, D.C., and microwave plasmas may also be used.
  • TFE tetrafluoroethylene
  • the process is applicable to a variety of other fluorocarbon monomers. These include, but are not limited to, hexafluoropropylene, perfluorobutene-2, chlorotrifluoroethylene, difluoroethylene, and the like.
  • a plasma reactor In its simplest form, a plasma reactor consists of an air-tight chamber with an inlet for monomer and an outlet to a vacuum pump. The chamber is fitted with either capacitor plates or an inductor coil. These may be placed inside or outside of the reactor in such fashion that the fields generated are sufficient to produce glow over a substantial region of the incoming monomer when connected to a frequency generator. Bell-jar and cylindrical flow through reactors are the most common.
  • Conditions such as pressure, monomer flow rate, power input and position of substrates relative to the glow are variables within the skill of the plasma polymerization art that depend upon the films desired and the reactor design.
  • TFE monomer is metered into the reaction chamber and into the glow region.
  • the power input into the glow region is set to maintain a deep violet glow. If a bluewhite glow is prevalent, a fluorine-poor polymer may result.
  • the substrate should be placed downstream and out of the glow region. It must be far enough from the glow so that the undesirable high energy species, including electrons, ions, metastables and UV photons, do not interfere with the free radical polymerization of TFE at the surface of the substrate.
  • the flow rate must be adjusted so that the desirable radicals can reach the substrate before terminating in the gas phase or attacking the reactor wall.
  • the pumping rate should be adjusted to give pressures in the range of 150-250 mtorr.
  • the inventors have found these general conditions to give films very similar to PTFE surfaces produced by other methods, as confirmed by contact angle measurements and Electron Spectroscopy for Chemical Analysis (ESCA).
  • ESCA is a major tool for surface analysis due to its low penetration of 50 Angstroms or less.
  • binding energy of inner shell electrons is measured which gives information about the elements on the surface.
  • the energy shift of the C 1s electron due to functional groups is too small for ESCA to be useful for structural analysis. Fluorine, however, produces energy shifts of about 2 eV per fluorine atom for the C 1s electron making ESCA quite useful for distinguishing functional groups containing fluorine.
  • the ESCA C 1s peak is split into series of peaks corresponding to --CF 3 (294 eV), --CF 2 --CF 2 (292 eV), --CF 2 --C--(290 eV), --CF--C--(288 eV) and groups of lower energy corresponding to hydrocarbons and carbon bound to --CF 2 . Shifts to higher energies for the peaks listed occur due to charging effects and must be corrected.
  • the first sample showed concentration of --CF 2 --C-- and --CF--C-- indicating fluorine abstraction and polymer cross-linking in the film resulting from the more undesirable, higher energy species.
  • the second sample showed response at 285 eV from methyl groups on the surface of the silicone rubber substrate and indicates a film of less than 50 Angstroms thick. Conditions similar to the second sample provide superior non-adherent films. These scans demonstrate the importance of positioning the samples sufficiently far from the glow.
  • Contact angles provide information about surface energy and have been found to correlate well with ESCA analysis.
  • the contact angle of a liquid on a solid surface increases as the surface energy decreases.
  • high contact angles reflect the liquid's inability to spread or wet the surface.
  • Visual contact angles are sufficient to compare the surface energies of the scans of the experimental samples to silicone rubber and PTFE.
  • Films polymerized under the conditions of the second experiment are indistinguishable from PTFE while the conditions of the first experiment give contact angles higher than silicone rubber but less than PTFE.
  • Critical surface tension measurements introduced by W. A. Zisman (Science 162:1360-1368, 1968) give the most reliable index of surface energy.
  • Construction of the check valve catheter begins with a silicone rubber catheter tube (0.090"OD ⁇ 0.015"ID) which is cut to the desired length. The end is plugged and exit ports are cut into the side of the tip. The area that the sleeve will cover is treated with a TFE plasma to eliminate adhesion of the sleeve to the catheter. A masking technique must be used to prevent TFE polymerization onto areas where it is not needed.
  • a sleeve of wall thickness 0.003" is cast around a mandrel 0.083" in diameter from silicone rubber.
  • the sleeve is trimmed to length and mounted onto the treated area of the catheter.
  • the sleeve is glued to the catheter by dipping into a liquid silicone rubber mixture, let cure and trimmed.
  • the squeeze fit between the sleeve and catheter provides a positive opening pressure and forms a uni-directional flow tip.
  • the TFE film has been the most dependable method to date to lubricate the sleeve and allows the catheter to remain only a two piece construction of silicone rubber.
  • a silicone rubber tube 0.052"ID ⁇ 0.062"OD is wrapped spirally around a small cylinder in a manner that flattens the tube and exposes one-half of its circumference. This is then treated with a TFE plasma. Upon removal from the cylinder, the result is a tube with one-half of its circumference over its whole length covered with a PTFE-like film. This is then dipped into a liquid silicone rubber mixture that gives a 0.100" overall catheter diameter when cured. The treated half of the wall easily separates from the dipped coating. After the inside wall is glued down at the tip, application of a vacuum to the inner lumen of the catheter collapses the inner wall forming the active state.

Abstract

Catheters for long term implantation having polymer surfaces in face-to-face contact which are provided with a thin film coating of a glow discharge plasma polymerized fluorocarbon to prevent adhesion of the contacting surfaces. The polymerized fluorocarbon film, between about 50 and 1000 Angstroms in thickness, is bonded to the substrate material giving a low surface energy without changing its bulk properties. The low surface energy will prevent adhesion of cured polymer surfaces in contact and act as a lubricant. The smooth pinhole-free films will control or prevent diffusion into or out of the bulk material. These biocompatible films provide an alternative use for polymers whose bulk properties are unacceptable but whose surface properties are desirable.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is directed to catheters adapted for long term implantation within living bodies and characterized by non-adherent contacting polymer surfaces. In some catheter designs, polymer films are in close contact with polymer surfaces. Two catheters of this type are disclosed in the copending Dorman application Ser. No. 245,379, filed Mar. 19, 1981, and the copending Wigness et al application Ser. No. 367,683, filed Apr. 12, 1982, hereafter referred to as the check valve catheter and the vascular access catheter, respectively. Both applications are of common ownership with the present application.
The preferred form of the check valve catheter consists of a thin silicone rubber sleeve stretched over a silicone rubber catheter. Silicone rubber surfaces in contact will adhere over time. This can result from the attraction of some compounds to chemically similar compounds and a knitting phenomenon where loose polymer chains at the surface become woven together. This adhesion greatly compromises the long term operation of the check valve catheter. During its development, a method of eliminating this adhesion was researched. A method of impregnating the rubber with a lubricant gave a temporary solution, but a permanent solid lubricant that would not leach out was desired. Films of graphite and albumin were sandwiched between the sleeve and the catheter but did not reduce adhesion significantly. Although silicone rubber has a low surface energy which is known to reduce adhesion, its ability to knit into a surface increases the actual surface contact causing a net increase of adhesion. For these reasons, a smooth film of lower surface energy than silicone rubber was desired.
The vascular access catheter consists of a flexible partition inside the catheter that can be shifted to one side to expose an inner lumen, thus enabling blood withdrawal or infusion. In its preferred form, it is made of silicone rubber and over time the contacting surfaces adhere to one another.
A fluorocarbon surface, such as polytetrafluoroethylene (PTFE) is known to have the desired nonadhering qualities. Glow discharge plasma polymerization of fluorocarbons is the only method known to provide the conditions necessary to react fluorine groups with the inert methyl groups on the surface of silicone rubber.
2. The Prior Art
Plasma polymerization of TFE has been widely studied in the last decade. Although most of the studies are aimed at understanding the process, a few specific applications have been cited and patents that include the process have been granted. U.S. Pat. No. 4,125,152, granted on Nov. 14, 1978, discloses the use of plasma polymerization of TFE to prevent adherent scale deposition on heat transfer surfaces in contact with heat transfer fluids. U.S. Pat. No. 4,100,113, granted on July 11, 1978, discloses the use of plasma polymerization of TFE in the preparation of electrolytic cell membranes by polymerization onto polymer substrates.
U.S. Pat. No. 3,703,585, granted on Nov. 21, 1972, discloses a process of sputtering PTFE polymer onto a substrate. This process differs from plasma polymerization of TFE in that a glow discharge using an inert gas such as argon is used to break off free radicals from the base material. The radicals are then able to deposit onto a substrate. This process has been studied for applying lubricant to small parts (K. G. Budinski, J. Vac. Sci. Technol. 12:786-789, 1975).
SUMMARY OF THE INVENTION
Broadly stated, the invention is directed to catheters for long term implantation within living bodies which are composed of flexible inert non-toxic biocompatible polymeric material and which have surfaces in close face-to-face contact. The catheters are characterized by a thin film glow discharge plasma polymerized fluorocarbon coating on at least one of the contacting surfaces. The ultra-thin coating having a thickness in the range between about 50 and 1000 Angstroms prevents adhesion of cured polymer surfaces in contact and acts as a lubricant. The films are smooth and pinhole-free so as to control or prevent diffusion into or out of the polymer substrate. The films are biocompatible and do not change the bulk properties of the substrate materials.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Methods of producing plasma polymerized coatings on surfaces from fluorocarbon monomers are widely known in the art. In carrying out the present invention, plasma polymerization is achieved by producing an electric glow discharge in a gas at ranges of 30-300 mtorr of pressure. A partially ionized gas or plasma is created when released electrons ionize the gas by inducing chain collisions. Radio frequency of 13.56 Mhz is most often used. However, audio frequency, 60 cycle, D.C., and microwave plasmas may also be used. When polymerization is carried out in the presence of a substrate, polymer is deposited uniformly on the exposed surfaces. While tetrafluoroethylene (TFE) is the preferred monomer, the process is applicable to a variety of other fluorocarbon monomers. These include, but are not limited to, hexafluoropropylene, perfluorobutene-2, chlorotrifluoroethylene, difluoroethylene, and the like.
In its simplest form, a plasma reactor consists of an air-tight chamber with an inlet for monomer and an outlet to a vacuum pump. The chamber is fitted with either capacitor plates or an inductor coil. These may be placed inside or outside of the reactor in such fashion that the fields generated are sufficient to produce glow over a substantial region of the incoming monomer when connected to a frequency generator. Bell-jar and cylindrical flow through reactors are the most common.
Conditions such as pressure, monomer flow rate, power input and position of substrates relative to the glow are variables within the skill of the plasma polymerization art that depend upon the films desired and the reactor design.
For high quality PTFE-like films, TFE monomer is metered into the reaction chamber and into the glow region. The power input into the glow region is set to maintain a deep violet glow. If a bluewhite glow is prevalent, a fluorine-poor polymer may result. The substrate should be placed downstream and out of the glow region. It must be far enough from the glow so that the undesirable high energy species, including electrons, ions, metastables and UV photons, do not interfere with the free radical polymerization of TFE at the surface of the substrate. The flow rate must be adjusted so that the desirable radicals can reach the substrate before terminating in the gas phase or attacking the reactor wall. Finally, the pumping rate should be adjusted to give pressures in the range of 150-250 mtorr. The inventors have found these general conditions to give films very similar to PTFE surfaces produced by other methods, as confirmed by contact angle measurements and Electron Spectroscopy for Chemical Analysis (ESCA).
ESCA is a major tool for surface analysis due to its low penetration of 50 Angstroms or less. In ESCA, binding energy of inner shell electrons is measured which gives information about the elements on the surface. In general, the energy shift of the C1s electron due to functional groups is too small for ESCA to be useful for structural analysis. Fluorine, however, produces energy shifts of about 2 eV per fluorine atom for the C1s electron making ESCA quite useful for distinguishing functional groups containing fluorine.
The ESCA C1s peak is split into series of peaks corresponding to --CF3 (294 eV), --CF2 --CF2 (292 eV), --CF2 --C--(290 eV), --CF--C--(288 eV) and groups of lower energy corresponding to hydrocarbons and carbon bound to --CF2. Shifts to higher energies for the peaks listed occur due to charging effects and must be corrected.
In a pair of experiments one sample was located 2 cm downstream of the glow with 2.3 watts input power and a flow rate of 35 cm3 min-1. The ESCA scan showed a large response at 292 eV (after adjusting for charging) and moderate responses at 294 eV, 290 eV, and 288 eV. The other sample was located 7.5 cm downstream with 3 watts input power and flow rate of 60 cm3 min-1 and showed much smaller responses at the latter three positions. The second sample showed high concentration of --CF2 --CF2 indicating polymerization by chain growth giving films similar to PTFE. The first sample showed concentration of --CF2 --C-- and --CF--C-- indicating fluorine abstraction and polymer cross-linking in the film resulting from the more undesirable, higher energy species. The second sample showed response at 285 eV from methyl groups on the surface of the silicone rubber substrate and indicates a film of less than 50 Angstroms thick. Conditions similar to the second sample provide superior non-adherent films. These scans demonstrate the importance of positioning the samples sufficiently far from the glow.
Contact angles provide information about surface energy and have been found to correlate well with ESCA analysis. The contact angle of a liquid on a solid surface increases as the surface energy decreases. Thus, high contact angles reflect the liquid's inability to spread or wet the surface. Visual contact angles are sufficient to compare the surface energies of the scans of the experimental samples to silicone rubber and PTFE. Films polymerized under the conditions of the second experiment are indistinguishable from PTFE while the conditions of the first experiment give contact angles higher than silicone rubber but less than PTFE. Critical surface tension measurements introduced by W. A. Zisman (Science 162:1360-1368, 1968) give the most reliable index of surface energy. Studies have reported critical surface tensions of 12 and 18 dynes/cm compared to 18 dynes/cm for PTFE under conditions similar to the plasma of the second experiment. (D. F. O'Kane et al, J. Macromol. Sci-Chem. A10:567-577, 1976, and B. D. Washo, J. Macromol. Sci-Chem. A10:559-566, 1976).
The manner in which the plasma polymerization process can be used in assembling the check valve catheter and the vascular access catheter is illustrated by the following.
Construction of the check valve catheter begins with a silicone rubber catheter tube (0.090"OD×0.015"ID) which is cut to the desired length. The end is plugged and exit ports are cut into the side of the tip. The area that the sleeve will cover is treated with a TFE plasma to eliminate adhesion of the sleeve to the catheter. A masking technique must be used to prevent TFE polymerization onto areas where it is not needed.
A sleeve of wall thickness 0.003" is cast around a mandrel 0.083" in diameter from silicone rubber. The sleeve is trimmed to length and mounted onto the treated area of the catheter. The sleeve is glued to the catheter by dipping into a liquid silicone rubber mixture, let cure and trimmed. The squeeze fit between the sleeve and catheter provides a positive opening pressure and forms a uni-directional flow tip. The TFE film has been the most dependable method to date to lubricate the sleeve and allows the catheter to remain only a two piece construction of silicone rubber.
To begin assembly of the vascular access catheter, a silicone rubber tube 0.052"ID×0.062"OD is wrapped spirally around a small cylinder in a manner that flattens the tube and exposes one-half of its circumference. This is then treated with a TFE plasma. Upon removal from the cylinder, the result is a tube with one-half of its circumference over its whole length covered with a PTFE-like film. This is then dipped into a liquid silicone rubber mixture that gives a 0.100" overall catheter diameter when cured. The treated half of the wall easily separates from the dipped coating. After the inside wall is glued down at the tip, application of a vacuum to the inner lumen of the catheter collapses the inner wall forming the active state. In this state, fluid can move through the catheter. The inner wall can then be shifted back thus displacing any fluid in the exposed lumen forming the dormant state. The film also prevents the post-curing adhesion of the silicone rubber surfaces. This manufacturing technique facilitates the construction of this catheter and improves the quality and dependability.
The prior patents, copending applications, and publications cited herein are incorporated by reference to the extent that might be necessary for a full and complete understanding of the present invention.
It is apparent that many modifications and variations of this invention as hereinbefore set forth may be made without departing from the spirit and scope thereof. The specific embodiments described are given by way of example only and the invention is limited only by the terms of the appended claims.

Claims (8)

We claim:
1. A catheter for long term implantation within a living body composed of concentric tubular elements of flexible inert non-toxic biocompatible polymeric material and having abutting surfaces between the concentric tubular elements in close face-to-face contact, said catheter characterized by the surface of at least one of said tubular elements having a thin film glow discharge plasma polymerized fluorocarbon coating to prevent adhesion to the contacting surface of the other concentric tubular element.
2. A catheter according to claim 1 wherein said coating is between about 50 and 1000 Angstroms thick.
3. A catheter according to claim 1 wherein said fluorocarbon is selected from the class consisting of tetrafluoroethylene, hexafluoropropylene, perfluorobutene-2, chlorotrifluoroethylene and difluoroethylene.
4. A catheter according to claim 1 wherein said catheter is composed of silicone rubber and said coating is polymerized from tetrafluoroethylene.
5. A method of treating catheters for long term implantation within a living body having concentric tubular elements with polymer surfaces between the tubular elements in face-to-face contact to prevent adhesion of the contacting surfaces, said method comprising applying a thin film glow discharge plasma polymerized biocompatible, fluorocarbon coating to the surface of at least one of said tubular elements prior to assembly of the catheter, and then assembling the catheter.
6. A method according to claim 5 wherein said coating is applied to a thickness of between about 50 to 1000 Angstroms.
7. A method according to claim 5 wherein said fluorocarbon is selected from the class consisting of tetrafluoroethylene, hexafluoropropylene, perfluorobutene-2, chlorotrifluoroethylene and difluoroethylene.
8. A method according to claim 5 wherein said catheter is composed of silicone rubber and said coating is polymerized from tetrafluoroethylene.
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Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0196821A2 (en) * 1985-03-25 1986-10-08 PMT Inc Tissue expander system
EP0228762A1 (en) * 1985-09-25 1987-07-15 Sherwood Medical Company Lubricant coated intubation device and method for the production thereof
US4826480A (en) * 1987-04-29 1989-05-02 Pacesetter Infusion, Ltd. Omentum diffusion catheter
US4846806A (en) * 1987-10-06 1989-07-11 501 Regents Of University Of Minnesota Implantable intravascular access system
US4849285A (en) * 1987-06-01 1989-07-18 Bio Med Sciences, Inc. Composite macrostructure of ceramic and organic biomaterials
US4875468A (en) * 1988-12-23 1989-10-24 Welch Allyn, Inc. Elastomer-ePTFE biopsy channel
US4876126A (en) * 1984-06-04 1989-10-24 Terumo Kabushiki Kaisha Medical instrument and method for making
US4884573A (en) * 1988-03-07 1989-12-05 Leocor, Inc. Very low profile angioplasty balloon catheter with capacity to use steerable, removable guidewire
US4909799A (en) * 1987-09-18 1990-03-20 Olav Thulesius Methods for preventing thrombosis; and surgical implant having reduced platelet deposition characteristics
US4921483A (en) * 1985-12-19 1990-05-01 Leocor, Inc. Angioplasty catheter
US4973493A (en) * 1982-09-29 1990-11-27 Bio-Metric Systems, Inc. Method of improving the biocompatibility of solid surfaces
WO1990014054A1 (en) * 1989-05-26 1990-11-29 Impra Inc. Non-porous coated ptfe graft
US4979959A (en) * 1986-10-17 1990-12-25 Bio-Metric Systems, Inc. Biocompatible coating for solid surfaces
EP0407965A1 (en) * 1989-07-10 1991-01-16 Terumo Kabushiki Kaisha Guide wire
WO1991009722A2 (en) * 1989-12-26 1991-07-11 Medtronic, Inc. Surface treatment for silicone tubing to improve slip properties
WO1991015251A1 (en) * 1990-04-02 1991-10-17 W.L. Gore & Associates, Inc. A catheter guidewire device having a covering of fluoropolymer tape
US5073171A (en) * 1989-01-12 1991-12-17 Eaton John W Biocompatible materials comprising albumin-binding dyes
US5100383A (en) * 1986-05-08 1992-03-31 Meir Lichtenstein Catheters permitting controlled diffusion
US5217492A (en) * 1982-09-29 1993-06-08 Bio-Metric Systems, Inc. Biomolecule attachment to hydrophobic surfaces
US5242389A (en) * 1990-07-19 1993-09-07 Sherwood Medical Company Enteral feeding tube enteral feeding tube with separate stylet lumen
US5258041A (en) * 1982-09-29 1993-11-02 Bio-Metric Systems, Inc. Method of biomolecule attachment to hydrophobic surfaces
US5263992A (en) * 1986-10-17 1993-11-23 Bio-Metric Systems, Inc. Biocompatible device with covalently bonded biocompatible agent
US5282851A (en) * 1987-07-07 1994-02-01 Jacob Labarre Jean Intraocular prostheses
US5342387A (en) * 1992-06-18 1994-08-30 American Biomed, Inc. Artificial support for a blood vessel
US5433909A (en) * 1992-03-13 1995-07-18 Atrium Medical Corporation Method of making controlled porosity expanded polytetrafluoroethylene products
US5512329A (en) * 1982-09-29 1996-04-30 Bsi Corporation Substrate surface preparation
US5513654A (en) * 1994-06-10 1996-05-07 New Designs Corporation Slip-resistant contraceptive male condom
US5534287A (en) * 1993-04-23 1996-07-09 Schneider (Europe) A.G. Methods for applying an elastic coating layer on stents
US5562638A (en) * 1993-06-21 1996-10-08 Baxter International Inc. Self-venting fluid system
US5702754A (en) * 1995-02-22 1997-12-30 Meadox Medicals, Inc. Method of providing a substrate with a hydrophilic coating and substrates, particularly medical devices, provided with such coatings
US5888591A (en) * 1996-05-06 1999-03-30 Massachusetts Institute Of Technology Chemical vapor deposition of fluorocarbon polymer thin films
US5897535A (en) * 1991-06-07 1999-04-27 Rtc, Inc. Non-contaminating probe and methods of making and using same
US6096564A (en) * 1999-05-25 2000-08-01 Wisconsin Alumni Research Foundation Plasma-aided treatment of surfaces against bacterial attachment and biofilm deposition
US6231600B1 (en) 1995-02-22 2001-05-15 Scimed Life Systems, Inc. Stents with hybrid coating for medical devices
US6258121B1 (en) 1999-07-02 2001-07-10 Scimed Life Systems, Inc. Stent coating
US6323256B1 (en) 1996-12-13 2001-11-27 Data Sciences International, Inc. Biocompatible medical devices with polyurethane surface
US6468649B1 (en) 1995-02-22 2002-10-22 Scimed Life Systems, Inc. Antimicrobial adhesion surface
US20020156434A1 (en) * 1998-03-13 2002-10-24 Minimed Inc. Stabilizing catheter for protein drug delivery
US6558798B2 (en) 1995-02-22 2003-05-06 Scimed Life Systems, Inc. Hydrophilic coating and substrates coated therewith having enhanced durability and lubricity
KR20030039568A (en) * 2001-11-13 2003-05-22 이영희 A method for manufacturing a needle for use with a motor-driven intramuscular stimulation needling device
WO2005094214A2 (en) 2004-03-02 2005-10-13 Sakhrani Vinay G Improved article with lubricated surface and method
US20060068224A1 (en) * 2004-09-30 2006-03-30 George Grobe Coated biomedical device and associated method
US20060122560A1 (en) * 2004-12-07 2006-06-08 Robert Burgmeier Medical devices and processes for preparing same
US20070235427A1 (en) * 2006-04-04 2007-10-11 Sakhrani Vinay G Apparatus and method for treating a workpiece with ionizing gas plasma
US20080044588A1 (en) * 2006-08-15 2008-02-21 Sakhrani Vinay G Method for Treating a Hydrophilic Surface
CN100431626C (en) * 2006-11-16 2008-11-12 暨南大学 Catheter for intraperitoneal chemotherapy
US20090010985A1 (en) * 2004-03-02 2009-01-08 Tribofilm Research, Inc. Article with Lubricated Surface and Method
US20090014551A1 (en) * 2007-07-13 2009-01-15 Bacoustics Llc Ultrasound pumping apparatus
US20090014550A1 (en) * 2007-07-13 2009-01-15 Bacoustics Llc Echoing ultrasound atomization and/or mixing system
FR2919589A1 (en) * 2007-08-01 2009-02-06 Airlessystems Soc Par Actions SHUTTER VALVE AND METHOD FOR MANUFACTURING SUCH CLAMP.
US20090126404A1 (en) * 2006-08-15 2009-05-21 Tribofilm Research, Inc. Method for Treating a Hydrophilic Surface
US20100174245A1 (en) * 2009-01-08 2010-07-08 Ward Dean Halverson System for pretreating the lumen of a catheter
US7896539B2 (en) 2005-08-16 2011-03-01 Bacoustics, Llc Ultrasound apparatus and methods for mixing liquids and coating stents
US20110148003A1 (en) * 2007-06-13 2011-06-23 Boston Scientific Scimed, Inc. Hardened polymeric lumen surfaces
EP2349034A1 (en) * 2008-10-24 2011-08-03 Gvd Corporation Coating methods, systems and related articles
US20120289895A1 (en) * 2011-03-28 2012-11-15 Achilleas Tsoukalis Fluids Exchanging System for Medical Use
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
US9101949B2 (en) 2005-08-04 2015-08-11 Eilaz Babaev Ultrasonic atomization and/or seperation system
US9119956B2 (en) 2012-11-21 2015-09-01 Cardiac Pacemakers, Inc. Medical electrodes with layered coatings
US9133412B2 (en) 2012-07-09 2015-09-15 Tribofilm Research, Inc. Activated gaseous species for improved lubrication
US9180289B2 (en) 2012-08-29 2015-11-10 Cardiac Pacemakers, Inc. Enhanced low friction coating for medical leads and methods of making
US20180333711A1 (en) * 2017-05-18 2018-11-22 GM Global Technology Operations LLC Self-cleaning film system and method of forming same
US10293105B2 (en) 2005-09-02 2019-05-21 Irras Ab Fluid exchange catheter system
US10533249B2 (en) 2017-05-18 2020-01-14 GM Global Technology Operations LLC Method of forming a self-cleaning film system
US10583428B2 (en) 2017-05-18 2020-03-10 GM Global Technology Operations LLC Self-cleaning film system and method of forming same
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US11448872B2 (en) 2017-05-31 2022-09-20 GM Global Technology Operations LLC Light-enhanced self-cleaning film system and method of forming same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2814296A (en) * 1954-04-15 1957-11-26 S & R J Everett & Co Ltd Surgical needles
US3703585A (en) * 1970-06-24 1972-11-21 Eastman Kodak Co D.c. sputtering of particulate polymeric compounds onto a substrate
US3922378A (en) * 1972-08-04 1975-11-25 Medical Evaluation Devices & I Fluorinated hydrocarbon coating method
US4100113A (en) * 1976-04-01 1978-07-11 Diamond Shamrock Corporation Electrolytic cell membrane and method of preparation by plasma polymerization of polyamide or polytetrafluoroethylene thin films onto polymeric substrates
US4125152A (en) * 1977-09-19 1978-11-14 Borg-Warner Corporation Scale resistant heat transfer surfaces and a method for their preparation
US4160454A (en) * 1975-07-09 1979-07-10 University Of Utah Implantable catheter system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2814296A (en) * 1954-04-15 1957-11-26 S & R J Everett & Co Ltd Surgical needles
US3703585A (en) * 1970-06-24 1972-11-21 Eastman Kodak Co D.c. sputtering of particulate polymeric compounds onto a substrate
US3922378A (en) * 1972-08-04 1975-11-25 Medical Evaluation Devices & I Fluorinated hydrocarbon coating method
US4160454A (en) * 1975-07-09 1979-07-10 University Of Utah Implantable catheter system
US4100113A (en) * 1976-04-01 1978-07-11 Diamond Shamrock Corporation Electrolytic cell membrane and method of preparation by plasma polymerization of polyamide or polytetrafluoroethylene thin films onto polymeric substrates
US4125152A (en) * 1977-09-19 1978-11-14 Borg-Warner Corporation Scale resistant heat transfer surfaces and a method for their preparation

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Silastic Intravenous Catheter"; Stewart et al.; The Bulletin of the Dow Corning Cent. for Aid to Med. Res.; Apr. 1962; pp. 5-6.
Chem. Abst.; vol. 95; 1981; No. 95: 209403q; "Thin Film Dep. by Plasma Poly. and Its App."; Hozumi et al.; Jitsumu Hyomen Gijutsu; 1981, 28(7); pp. 318-323 (Japanese).
Chem. Abst.; vol. 95; 1981; No. 95: 209403q; Thin Film Dep. by Plasma Poly. and Its App. ; Hozumi et al.; Jitsumu Hyomen Gijutsu; 1981, 28(7); pp. 318 323 (Japanese). *
K. G. Budinski, J. Vac. Sci. Technol., 12:786 789, 1975. *
K. G. Budinski, J. Vac. Sci. Technol., 12:786-789, 1975.
Silastic Intravenous Catheter ; Stewart et al.; The Bulletin of the Dow Corning Cent. for Aid to Med. Res.; Apr. 1962; pp. 5 6. *

Cited By (116)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5258041A (en) * 1982-09-29 1993-11-02 Bio-Metric Systems, Inc. Method of biomolecule attachment to hydrophobic surfaces
US5512329A (en) * 1982-09-29 1996-04-30 Bsi Corporation Substrate surface preparation
US4973493A (en) * 1982-09-29 1990-11-27 Bio-Metric Systems, Inc. Method of improving the biocompatibility of solid surfaces
US5741551A (en) * 1982-09-29 1998-04-21 Bsi Corporation Preparation of polymeric surfaces
US5217492A (en) * 1982-09-29 1993-06-08 Bio-Metric Systems, Inc. Biomolecule attachment to hydrophobic surfaces
US4876126A (en) * 1984-06-04 1989-10-24 Terumo Kabushiki Kaisha Medical instrument and method for making
EP0196821A3 (en) * 1985-03-25 1988-10-26 PMT Inc Tissue expander system
EP0196821A2 (en) * 1985-03-25 1986-10-08 PMT Inc Tissue expander system
US4685447A (en) * 1985-03-25 1987-08-11 Pmt Corporation Tissue expander system
EP0228762A1 (en) * 1985-09-25 1987-07-15 Sherwood Medical Company Lubricant coated intubation device and method for the production thereof
AU584742B2 (en) * 1985-09-25 1989-06-01 Sherwood Medical Company Lubricant composition, method of coating and a coated lubricant intubation device
US4705709A (en) * 1985-09-25 1987-11-10 Sherwood Medical Company Lubricant composition, method of coating and a coated intubation device
US4921483A (en) * 1985-12-19 1990-05-01 Leocor, Inc. Angioplasty catheter
US5100383A (en) * 1986-05-08 1992-03-31 Meir Lichtenstein Catheters permitting controlled diffusion
US4979959A (en) * 1986-10-17 1990-12-25 Bio-Metric Systems, Inc. Biocompatible coating for solid surfaces
US5263992A (en) * 1986-10-17 1993-11-23 Bio-Metric Systems, Inc. Biocompatible device with covalently bonded biocompatible agent
US4826480A (en) * 1987-04-29 1989-05-02 Pacesetter Infusion, Ltd. Omentum diffusion catheter
US4849285A (en) * 1987-06-01 1989-07-18 Bio Med Sciences, Inc. Composite macrostructure of ceramic and organic biomaterials
US5282851A (en) * 1987-07-07 1994-02-01 Jacob Labarre Jean Intraocular prostheses
US4909799A (en) * 1987-09-18 1990-03-20 Olav Thulesius Methods for preventing thrombosis; and surgical implant having reduced platelet deposition characteristics
US4846806A (en) * 1987-10-06 1989-07-11 501 Regents Of University Of Minnesota Implantable intravascular access system
US4884573A (en) * 1988-03-07 1989-12-05 Leocor, Inc. Very low profile angioplasty balloon catheter with capacity to use steerable, removable guidewire
US4875468A (en) * 1988-12-23 1989-10-24 Welch Allyn, Inc. Elastomer-ePTFE biopsy channel
US5073171A (en) * 1989-01-12 1991-12-17 Eaton John W Biocompatible materials comprising albumin-binding dyes
WO1990014054A1 (en) * 1989-05-26 1990-11-29 Impra Inc. Non-porous coated ptfe graft
EP0407965A1 (en) * 1989-07-10 1991-01-16 Terumo Kabushiki Kaisha Guide wire
WO1991009722A3 (en) * 1989-12-26 1991-08-22 Medtronic Inc Surface treatment for silicone tubing to improve slip properties
WO1991009722A2 (en) * 1989-12-26 1991-07-11 Medtronic, Inc. Surface treatment for silicone tubing to improve slip properties
WO1991015251A1 (en) * 1990-04-02 1991-10-17 W.L. Gore & Associates, Inc. A catheter guidewire device having a covering of fluoropolymer tape
US5242389A (en) * 1990-07-19 1993-09-07 Sherwood Medical Company Enteral feeding tube enteral feeding tube with separate stylet lumen
US5897535A (en) * 1991-06-07 1999-04-27 Rtc, Inc. Non-contaminating probe and methods of making and using same
US5433909A (en) * 1992-03-13 1995-07-18 Atrium Medical Corporation Method of making controlled porosity expanded polytetrafluoroethylene products
US5980799A (en) * 1992-03-13 1999-11-09 Atrium Medical Corporation Methods of making controlled porosity expanded polytetrafluoroethylene products and fabrication
US5861033A (en) * 1992-03-13 1999-01-19 Atrium Medical Corporation Method of making controlled porosity expanded polytetrafluoroethylene products and fabrication
US5342387A (en) * 1992-06-18 1994-08-30 American Biomed, Inc. Artificial support for a blood vessel
US5607445A (en) * 1992-06-18 1997-03-04 American Biomed, Inc. Stent for supporting a blood vessel
US5534287A (en) * 1993-04-23 1996-07-09 Schneider (Europe) A.G. Methods for applying an elastic coating layer on stents
US6375787B1 (en) 1993-04-23 2002-04-23 Schneider (Europe) Ag Methods for applying a covering layer to a stent
US5814025A (en) * 1993-06-21 1998-09-29 Baxter International Inc. Self-venting fluid system
US5562638A (en) * 1993-06-21 1996-10-08 Baxter International Inc. Self-venting fluid system
US5513654A (en) * 1994-06-10 1996-05-07 New Designs Corporation Slip-resistant contraceptive male condom
US6709706B2 (en) 1995-02-22 2004-03-23 Scimed Life Systems, Inc. Hydrophilic coating and substrates coated therewith having enhanced durablity and lubricity
US6048620A (en) * 1995-02-22 2000-04-11 Meadox Medicals, Inc. Hydrophilic coating and substrates, particularly medical devices, provided with such a coating
US6558798B2 (en) 1995-02-22 2003-05-06 Scimed Life Systems, Inc. Hydrophilic coating and substrates coated therewith having enhanced durability and lubricity
US5702754A (en) * 1995-02-22 1997-12-30 Meadox Medicals, Inc. Method of providing a substrate with a hydrophilic coating and substrates, particularly medical devices, provided with such coatings
US6468649B1 (en) 1995-02-22 2002-10-22 Scimed Life Systems, Inc. Antimicrobial adhesion surface
US6231600B1 (en) 1995-02-22 2001-05-15 Scimed Life Systems, Inc. Stents with hybrid coating for medical devices
US6153269A (en) * 1996-05-06 2000-11-28 Massachusetts Institute Of Technology Chemical vapor deposition of fluorocarbon polymer thin films
US6156435A (en) * 1996-05-06 2000-12-05 Massachusetts Institute Of Technology Chemical vapor deposition of fluorocarbon polymer thin films
US5888591A (en) * 1996-05-06 1999-03-30 Massachusetts Institute Of Technology Chemical vapor deposition of fluorocarbon polymer thin films
US6323256B1 (en) 1996-12-13 2001-11-27 Data Sciences International, Inc. Biocompatible medical devices with polyurethane surface
US20020111393A1 (en) * 1996-12-13 2002-08-15 Data Sciences International, Inc. Biocompatible medical devices with polyurethane surface
US6774157B2 (en) 1996-12-13 2004-08-10 Transoma Medical, Inc. Biocompatible medical devices with polyurethane surface
US20020156434A1 (en) * 1998-03-13 2002-10-24 Minimed Inc. Stabilizing catheter for protein drug delivery
US6096564A (en) * 1999-05-25 2000-08-01 Wisconsin Alumni Research Foundation Plasma-aided treatment of surfaces against bacterial attachment and biofilm deposition
US6258121B1 (en) 1999-07-02 2001-07-10 Scimed Life Systems, Inc. Stent coating
US6569195B2 (en) 1999-07-02 2003-05-27 Scimed Life Systems, Inc. Stent coating
EP1423157A2 (en) * 2001-09-05 2004-06-02 Medtronic MiniMed, Inc. Stabilizing catheter for protein drug delivery
EP1423157A4 (en) * 2001-09-05 2006-03-08 Medtronic Minimed Inc Stabilizing catheter for protein drug delivery
KR20030039568A (en) * 2001-11-13 2003-05-22 이영희 A method for manufacturing a needle for use with a motor-driven intramuscular stimulation needling device
US20080145565A1 (en) * 2003-05-06 2008-06-19 Sakhrani Vinay G Article with Lubricated Surface and Method
US7674504B2 (en) 2003-05-06 2010-03-09 Sakhrani Vinay G Article with lubricated surface and method
US7553529B2 (en) 2003-05-06 2009-06-30 Tribofilm Research, Inc. Article with lubricated surface and method
US20080254304A1 (en) * 2003-05-06 2008-10-16 Tribofilm Research, Inc. Article with Lubricated Surface and Method
US7431989B2 (en) 2003-05-06 2008-10-07 Tribofilm Research, Inc. Article with lubricated surface and method
EP2676741A2 (en) 2004-03-02 2013-12-25 Tribofilm Research, Inc. Improved article with lubricated surface and method
WO2005094214A2 (en) 2004-03-02 2005-10-13 Sakhrani Vinay G Improved article with lubricated surface and method
US20090010985A1 (en) * 2004-03-02 2009-01-08 Tribofilm Research, Inc. Article with Lubricated Surface and Method
US8124207B2 (en) 2004-03-02 2012-02-28 Sakhrani Vinay G Article with lubricated surface and method
EP1642653A3 (en) * 2004-09-30 2007-04-04 DePuy Products, Inc. Coated biomedical device and associated method
US20060068224A1 (en) * 2004-09-30 2006-03-30 George Grobe Coated biomedical device and associated method
EP1642653A2 (en) * 2004-09-30 2006-04-05 DePuy Products, Inc. Coated biomedical device and associated method
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US20060122560A1 (en) * 2004-12-07 2006-06-08 Robert Burgmeier Medical devices and processes for preparing same
US9101949B2 (en) 2005-08-04 2015-08-11 Eilaz Babaev Ultrasonic atomization and/or seperation system
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US20110148003A1 (en) * 2007-06-13 2011-06-23 Boston Scientific Scimed, Inc. Hardened polymeric lumen surfaces
US8449803B2 (en) * 2007-06-13 2013-05-28 Boston Scientific Scimed, Inc. Method of forming a catheter
US7780095B2 (en) 2007-07-13 2010-08-24 Bacoustics, Llc Ultrasound pumping apparatus
US20090014551A1 (en) * 2007-07-13 2009-01-15 Bacoustics Llc Ultrasound pumping apparatus
US7753285B2 (en) 2007-07-13 2010-07-13 Bacoustics, Llc Echoing ultrasound atomization and/or mixing system
US20090014550A1 (en) * 2007-07-13 2009-01-15 Bacoustics Llc Echoing ultrasound atomization and/or mixing system
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US8882707B2 (en) * 2011-03-28 2014-11-11 Micrel Medical Devices S.A. Fluids exchanging system for medical use
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US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
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